Adhesion of tungsten nitride films to a silicon surface

ABSTRACT

A process is described that forms a low resistivity connection between a tungsten layer and a silicon surface with high adherence of the tungsten to the silicon. The silicon surface is plasma-cleaned to remove native oxide. A very thin layer (one or more monolayers) of Si—NH 2  is formed on the silicon surface, serving as an adhesion layer. A WN x  layer is formed over the Si—NH 2  layer, using an atomic layer deposition (ALD) process, to serve as a barrier layer. A thick tungsten layer is formed over the WN x  layer by CVD. An additional metal layer (e.g., aluminum) may be formed over the tungsten layer.

FIELD OF THE INVENTION

This invention relates to semiconductor processing and, in particular, to forming a low resistivity and high adherence interface between a tungsten layer and a silicon surface.

BACKGROUND

Tungsten (W) is a common metal used for conductors on a silicon wafer. A tungsten layer is typically formed using a CVD process where WF₆+SiH₄ (silane) gases react to leave a layer of tungsten on a surface. Tungsten is not directly deposited on silicon since the fluorine in the WF₆ reacts with the silicon to degrade the adhesion of the tungsten layer and etches the silicon surface. Additionally, the W atoms will migrate into the silicon.

It is known to form a thin oxide layer on the silicon surface and then form the tungsten layer over the oxide. This results in a thick tungsten layer, a thin WO_(x) interface layer, and a thin oxide layer beneath the surface of the wafer. The WO_(x) and oxide layers are highly resistive, resulting in poor electrical contact between the tungsten layer and the silicon.

Accordingly, a non-tungsten barrier layer (e.g., Ti) is typically formed between the tungsten layer and the silicon, as shown in FIG. 1.

FIG. 1 is a cross-sectional view of one application of using tungsten to electrically contact silicon. An oxide layer 10 formed over a silicon substrate 12 is etched to expose a portion of the silicon. The exposed portion may be a doped region of an electronic device, such as a transistor or diode, or any other silicon region. A multi-layered barrier layer 14 of Ti/TiN is first formed over the silicon to improve adhesion of the overlying tungsten layer, protect the silicon from fluorine during the subsequent WF₆ exposure, and block W atoms from migrating into the silicon.

A conventional CVD tungsten deposition process is then performed to form a relatively thick layer of tungsten 16. The tungsten layer may be patterned and etched for defining a conductive plug for being contacted by a subsequent aluminum layer or for otherwise forming a conductor to other components.

Forming the Ti/TiN barrier requires steps that significantly add to the cost of processing the wafer.

SUMMARY

A process is described that does not use any non-tungsten barrier layer between silicon and a tungsten layer, yet the process forms a low resistivity connection between the tungsten layer and the silicon with high adherence of the tungsten to the silicon.

The process steps in one embodiment are as follows.

The silicon surface is plasma-cleaned to remove native oxide.

A very thin layer (one or more monolayers) of Si—NH₂ is formed on the silicon surface by introducing a NH based gas at the end of the cleaning process. This layer serves primarily as an adhesion layer.

Using an atomic layer deposition (ALD) process, a WN_(x) layer is formed over the Si—NH₂ layer using WF₆ and a nitrogen based gas. All or a portion of the NH₂ layer may be converted to WN_(x). This layer serves primarily as a barrier layer.

Optionally, the WN_(x) layer surface is treated using a nitrogen based gas to create additional barrier layers for additional protection of the silicon.

A thick tungsten layer is then formed over the WN_(x) layer by CVD.

The above process results in a higher quality contact than achieved in prior processes, and the process is highly efficient and reliable.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a prior art barrier layer between tungsten and silicon.

FIG. 2 is a flowchart of one embodiment of the inventive process for forming a barrier layer.

FIGS. 3, 4, 5, and 6 are cross-sectional views of a silicon wafer undergoing the inventive process.

FIG. 7 illustrates an aluminum layer formed over the patterned tungsten layer.

Elements with the same numbers in the various figures are the same.

DETAILED DESCRIPTION

FIG. 2 identifies the basic steps in the process for creating a high quality contact between tungsten and silicon, and FIGS. 3–6 illustrate the process being performed on a silicon wafer.

FIG. 3 illustrates a standard silicon substrate 20 having deposited over it an oxide layer 22. The oxide layer 22 is not relevant to the invention but illustrates a typical use of tungsten in semiconductor processing. Tungsten is commonly used as a conductive plug to fill a trench or hole formed in oxide and act as an interface between the silicon and an aluminum layer, where the aluminum layer provides the main conductive paths for the integrated circuit. The exposed silicon is usually a doped region forming part of a semiconductor device such as a transistor or diode.

In step 24 of FIG. 2, the wafer of FIG. 3 is placed in a conventional plasma cleaning chamber to remove any native oxide from the exposed silicon surface 26. The plasma cleaning chamber may use inductively coupled plasma (ICP) to clean the silicon using energized argon ions. In one embodiment, the Ar gas flow is 20 sccm, the power is 500 W-s, the mean bias on the wafer is 300 W, and the etch is conducted for 12.5 seconds. Many other cleaning techniques are also suitable.

Examples of creating a plasma for cleaning a wafer are found in U.S. Pat. Nos. 6,630,201 and 5,180,432, and U.S. patent application Publication US 2002/0160125 A1, all incorporated herein by reference.

In step 28, a thin Si—NH₂ layer 30 (FIG. 4) is formed on the substrate 20 to enhance adhesion of the subsequent WN_(x) layer. The Si—NH₂ layer 30 is formed in the cleaning chamber by flowing Ar, H₂, and N₂ gas at a rate of 20 sccm, with a power of 750 W-s, for less than one minute. In one embodiment, the gas was flowed for between 1–5 seconds with good results. The wafer is not biased. The resulting thickness of the Si—NH₂ layer 30 is on the order of monolayers, such as 1–3 nm. Since the silicon becomes part of the composition, the Si—NH₂ layer 30 extends below the wafer surface.

In another embodiment, the gas flowed may be any combination of H₂/N₂, H₂/NH₃, NH₃, WF₆/N₂, with or without plasma at a high wafer temperature.

NH₂ is called an amide, so forming the Si—NH₂ layer 30 is referred to as amidating this Si surface.

Since SiN_(x) is resistive, the Si—NH₂ layer 30 should be only as thick as necessary for adequate adhesive of the WN_(x) layer.

In step 32, the wafer is removed from the cleaning chamber and placed in an atomic layer deposition (ALD) chamber. If the cleaning chamber can also perform ALD, then the wafer does not have to be transferred to another chamber.

Cycles of gases B₂H₆→WF₆→NH₃ are introduced into the ALD chamber. These gases react at the surface of the wafer to form a monolayer (e.g., 1 Å) of WN_(x) each cycle. The entire Si—NH₂ layer 30 is preferably converted into a layer of WN_(x). The adhesion of WN_(x) to the silicon is strong due to covalent bonding.

The ALD process is repeated to form a WN_(x) layer 34 of any thickness. For example, there may be on the order of 50 cycles to achieve the desired thickness (e.g., 50 Å). In one embodiment, the thickness is 30–100 Å. A thicker WN_(x) layer 34 provides additional protection of the silicon surface from fluoride in the WF₆. In one embodiment, x is 4 or 5.5; however, a viable range of x is between 1 and 6.

Optionally, a first cycle of NH₃→WF₆ may improve the first monolayer of WN_(x) prior to the B₂H₆→WF₆→NH₃ cycles.

Optionally, as shown in step 36, after the 50 Å WN_(x) layer 34 is formed, any combination of N₂, H₂/N₂, NH₃, N₂O gases are introduced to form a nitrogen based monolayer on the top surface of the WN_(x) layer 34. When the thick W layer is subsequently deposited, an additional WN_(x) barrier layer (a monolayer) will be formed to provide additional protection of the silicon.

Suitable ALD reactors are commercially available.

In step 38, the wafer is placed in a CVD chamber, and a thick W layer 40 is formed by flowing WF₆ and SiH₄ gases. In one embodiment, the thickness is 400 Å. The W layer 40 may be patterned for use as a plug or for another use.

In one example, as shown in FIG. 7, the W layer 40 is patterned by etching, and an aluminum layer 42 is deposited over the patterned W layer to form a conductor pattern for an integrated circuit.

The silicon is protected from the W layer 40 and the fluorine by the WN_(x) barrier layer, and the barrier layer provides good adhesion for the W layer 40 with very low resistivity.

Having described the invention in detail, those skilled in the art will appreciate that, given the present disclosure, modifications may be made to the invention without departing from the spirit and invention concepts described herein. Therefore, it is not intended that the scope of the invention be limited to the specific embodiments illustrated and described. 

1. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface, wherein removing the native oxide comprises cleaning he silicon surface using a plasma etch; forming a first nitrogen-containing layer on the silicon surface; forming a first WN_(x) layer over the nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer.
 2. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface, wherein forming the first nitrogen-containing layer comprises introducing a nitrogen-based gas into a cleaning chamber used to remove the native oxide from the silicon surface; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer.
 3. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface, wherein forming the first nitrogen-containing layer on the silicon surface comprises forming a Si—NH₂ layer on the silicon surface; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer.
 4. The method of claim 3 wherein forming a Si—NH₂ layer comprises flowing Ar, H₂, and N₂ gas into a cleaning chamber for less than one minute.
 5. The method of claim 4 wherein forming a Si—NH₂ layer comprises flowing Ar, H₂, and N₂ gas into a cleaning chamber for 5 seconds or less.
 6. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a nitrogen-containing layer on the silicon surface; and forming a WN_(x) layer over the nitrogen-containing layer by atomic layer deposition, the WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; and depositing a tungsten layer over the WN_(x) layer; wherein forming the WN_(x) layer comprises: introducing a first cycle of gases NH₃→WF₆ into an ALD chamber to form a first WN_(x) monolayer; and introducing cycles of gases B₂H₆→WF₆→NH₃ into the ALD chamber to form successive second layers of WN_(x) over the first WN_(x) monolayer until the second layers of WN_(x) are of a desired thickness.
 7. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer, wherein depositing a tungsten layer directly over the second nitrogen-containing layer comprises flowing WF₆ and SiH₄ in a CVD chamber.
 8. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer; and etching the tungsten layer to form a patterned tungsten interface between the silicon surface and a metal layer.
 9. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface, wherein forming a first nitrogen-containing layer comprises forming a first nitrogen-containing layer from about 1 nm to 3 nm thick; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer.
 10. The method of claim 8 wherein forming a first WN_(x) layer comprises forming a first WN_(x) layer from about 30 Å to 100 Å thick.
 11. A method for forming a conductor on a silicon surface comprising: removing native oxide from the silicon surface; forming a first nitrogen-containing layer on the silicon surface; forming a first WN_(x) layer over the first nitrogen-containing layer by atomic layer deposition, the first WN_(x) layer forming a barrier layer, wherein x is between 1 and 6; forming a second nitrogen-containing layer over the surface of the first WN_(x) layer, forming the second nitrogen-containing layer comprising providing a gas that contains nitrogen, but no gases containing tungsten, to the top surface of the first WN_(x) layer; and depositing a tungsten layer directly over the second nitrogen-containing layer, the tungsten layer reacting with the second nitrogen-containing layer so as to form a second WN_(x) layer over the first WN_(x) layer for additional protection of the silicon, depositing the tungsten layer over the second nitrogen-containing layer also forming a tungsten layer over the second WN_(x) layer, where the tungsten layer over the second WN_(x) layer does not contain nitrogen and acts as a highly conductive layer, the tungsten layer not containing nitrogen being thicker than the first WN_(x) layer and the second WN_(x) layer.
 12. The method of claim 11 wherein forming a second nitrogen-containing layer over the surface of the first WN_(x) layer comprises exposing the surface of the first WN_(x) layer to the gas that contains nitrogen.
 13. The method of claim 11 wherein forming a second nitrogen-containing layer over the surface of the first WN_(x) layer comprises forming a second nitrogen-containing layer directly on the surface of the first WN_(x) layer. 